Photosensitive compound and photosensitive composition

ABSTRACT

The present invention relates to a water-soluble photosensitive compound represented by the general formula (1): 
                 
 
or by the general formula (2): 
                 
 
in the formula, X represents a direct bond, an alkylene group containing 1 to 5 carbon atoms, —CH 2 O—, —OCH 2 —, —CH 2 OCH 2 —, —O—, —S— or —SO 2 —, and Z represents —SO 3   − .Q + , —COO − .Q +  or —SO 2 NR 2 , in which Q +  represents Li + , Na + , K +  or N + R 4  and R represents a hydrogen atom and/or an alkyl group containing 1 to 5 carbon atoms, said alkyl group optionally having one hydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group,
 
wherein a photosensitive group has an absorption maximum wavelength of not longer than 305 nm in the ultraviolet absorption spectrum thereof.

TECHNICAL FIELD

The present invention relates to a photosensitive compound and aphotosensitive composition and, more particularly, it relates to awater-soluble photosensitive compound having an ultraviolet absorptionmaximum assignable to a photosensitive group in the short wavelengthultraviolet region and to a water-soluble photosensitive compositioncomprising said compound.

BACKGROUND ART

In the art, photosensitive compositions are used as materials forforming desired fine patterns by exposure to ultraviolet rays or likeactive energy beams.

As regards photosensitive compositions containing an azide compound,among others, Japanese Kokai Publication Sho-48-79970 discloses aphotosensitive composition comprising polyvinylpyrrolidone and an azidecompound and Japanese Kokai Publication Sho-50-33764 discloses aphotosensitive composition comprising an acrylamide-diacetone acrylamidecopolymer and an azide compound.

Stilbene-based azide compounds are used as the azide compounds in theabove photosensitive compositions. The stilbene-based azides have anabsorption maximum wavelength of 335 nm or longer, and thephotosensitive compositions containing such azide compounds showsatisfactory resolution upon close contact exposure but have a problemin that, upon proximity exposure, they cannot show satisfactoryresolution. It has thus been earnestly desired that the resolution beimproved.

DISCLOSURE OF INVENTION

As a result of intensive investigations made by the present inventors tosolve such problem with the prior art photosensitive compositions, itwas found that a water-soluble photosensitive composition containing awater-soluble photosensitive compound whose photosensitive group has anabsorption maximum wavelength of 305 nm or shorter in the ultravioletabsorption spectrum thereof show very high resolution. Such finding hasnow led to completion of the present invention.

Thus, the present invention provides a water-soluble photosensitivecompound represented by the following general formula (1):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂—, Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄ and R represents a hydrogen atom and/or an alkyl groupcontaining 1 to 5 carbon atoms, said alkyl group optionally having onehydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group, and the twoZ groups may be the same or different or by the following generalformula (2):

in the formula, X represents a direct bond, an alkylene group-containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂— and Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄ and R represents a hydrogen atom and/or an alkyl groupcontaining 1 to 5 carbon atoms, said alkyl group optionally having onehydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group,

-   -   wherein a photosensitive group has an absorption maximum        wavelength of not longer than 305 nm in the ultraviolet        absorption spectrum thereof;    -   and a water-soluble photosensitive composition    -   comprising 1 to 30% by mass of a water-soluble photosensitive        compound (A) and 70 to 99% by mass of a water-soluble vinyl        (co)polymer (B),    -   wherein a photosensitive group in said (A) has an absorption        maximum wavelength of not longer than 305 nm in the ultraviolet        absorption spectrum thereof.

The C₁₋₅ alkylene group represented by X in the general formula (1) or(2) includes straight-chain alkyl groups such as methylene, ethylene,n-propylene, n-butylene, n-pentylene, etc.; and branched alkylene groupssuch as 1-methylethylene, 1-methylpropylene, 2-methylpropylene,1-methylbutylene, 2-methylbutylene, 1,1-dimethylpropylene,2,2-dimethylpropylene, etc.

Preferred as X in the general formula (1) or (2) are a direct bond, C₁₋₅alkylene groups, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂—. Morepreferred are a direct bond, methylene and ethylene.

In the general formula (1) or (2), Z is —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂.Q⁺ includes Li⁺, Na⁺, K⁺ and N⁺R, and, as R, there may be mentioned ahydrogen atom and/or C₁₋₅ alkyl groups such as methyl, ethyl, n- andi-propyl, n-, iso- and tert-butyl, n-pentyl, 2-methylbutyl and3-methylbutyl; and C₁₋₅ alkyl groups having one hydroxy, ether,carbonyl, carbonyloxy or oxycarbonyl group, for example hydroxyalkylgroups such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl,2-hydroxypropyl, 3-hydroxy-l-methylpropyl, 4-hydroxybutyl and5-hydroxypentyl; hydroxyalkoxyalkyl groups such as2-(2-hydroxyethoxy)ethyl; alkoxyalkyl groups such as methoxymethyl,2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,3-propoxypropyl and 3-butoxybutyl; alkylcarbonyl(oxy)alkyl groups suchas methylcarbonylmethyl, methylcarbonylethyl, methylcarbonylpropyl,methylcarbonyloxymethyl, methylcarbonyloxyethyl andmethylcarbonyloxypropyl; alkoxycarbonylalkyl groups such asmethyloxycarbonylmethyl, methyloxycarbonylethyl andmethyLoxycarbonylpropyl; and so forth.

Among these, from the solubility viewpoint, preferred are —SO₃ ⁻.Q⁺groups (in which Q⁺ represents Li⁺, Na⁺, K⁺ or N⁺R₄ and R represents ahydrogen atom and/or a C₁₋₅ alkyl group which may optionally have onehydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group, and theplural R groups may be the same or different). Particularly preferredare —SO₃ ⁻.Na⁺, —SO₃ ⁻.K⁺ or —SO₃ ⁻.NR₄ ⁺.

The absorption maximum wavelength, in the ultraviolet absorptionspectrum, of the photosensitive group in the water-solublephotosensitive compound of the invention as represented by the generalformula (1) or (2) is generally not longer than 305 nm and, in caseswhere a high pressure mercury lamp or super-high pressure mercury lampis used as the exposure light source, it is preferably 240 to 300 nmfrom the viewpoint of matching between exposure light intensity andresolution.

The “absorption maximum wavelength, in the ultraviolet absorptionspectrum, of a photosensitive group” means the absorption maximumwavelength of a photosensitive functional group [e.g. the azide group inthe general formula (1) or (2)] and no consideration is given to theabsorption maximum wavelength(s) of a nonphotosensitive functionalgroup(s).

Preferred among the photosensitive compounds of the present invention asrepresented by the general formula (1) or (2) from resolution,sensitivity and solubility viewpoints are disodium4,4′-diazido-2,2′-biphenylenedisulfonate, disodium4,4′-diazido-3,3′-biphenylenedisulfonate, disodium4,4′-diazido-2,2′-methylenedibenzenedisulfonate, disodium4,4′-diazido-3,3′-methylenedibenzenedisulfonate, disodium4,4′-diazido-2,2′-(1,2-ethanediyldibenzene)disulfonate and disodium4,4′-diazido-3,3′-(1,2-ethanediyldibenzene)disulfonate.

The processes for producing the photosensitive compounds of theinvention as represented by the general formula (1) or (2) are describedin the following.

1. When Z in the general formula (1) is —SO₃ ⁻.Q⁺ (Q⁺ being Li⁺, Na⁺ orK⁺)

(1) When X in the general formula (1) is a direct bond:

A 2-nitrobenzenesulfonic acid derivative (e.g. sodium2-nitrobenzenesulfonate) or a 3-nitrobenzenesulfonic acid derivative(e.g. sodium 3-nitrobenzenesulfonate) is treated with zinc dust in thepresence of an alkali (e.g. sodium hydroxide) and the resultinghydrazobenzene derivative is treated with sulfuric acid to give thecorresponding 4,4′-diaminobiphenyl derivative. This is diazotized usingsodium nitrite under acidic conditions in the presence of hydrochloricacid, followed by reaction with sodium azide, to give the desiredproduct.

(2) When X in the general formula (1) is a methylene group:

An 2-anilinesulfonic acid derivative (e.g. sodium 2-anilinesulfonate) oran 3-anilinesulfonic acid derivative (e.g. sodium 3-anilinesulfonate) istreated with formalin under acidic conditions to give the corresponding4,4′-diaminodiphenylmethane derivative. This is diazotized using sodiumnitrite under acidic conditions in the presence of hydrochloric acid,followed by reaction with sodium azide, to give the desired product.

(3) When X in the general formula (1) is an alkylene group containing 2to 5 carbon atoms:

A 2-nitrobenzenesulfonic acid derivative (e.g. sodium2-nitrobenzenesulfonate) or a 3-nitrobenzenesulfonic acid derivative.(e.g. sodium 3-nitrobenzenesulfonate) is treated with a C₂₋₅ α,ω-dichloroalkylene in the presence of aluminum chloride, followed byhydrogenation using palladium-carbon, to give the corresponding4,4′-diaminodiphenyl-C₂₋₅-alkylene derivative. This is diazotized usingsodium nitrite under acidic conditions in the presence of hydrochloricacid, followed by reaction with sodium azide, to give the desiredproduct.

(4) When X in the general formula (1) is —CH₂O— or —OCH₂—:

A 5-chloromethyl-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzenesulfonate) or a2-chloromethyl-5-nitrobenzenesulfonic acid derivative (e.g. sodium2-chloromethyl-5-nitrobenzenesulfonate) is reacted with a5-hydroxy-2-nitrobenzenesulfonic acid derivative or a2-hydroxy-5-nitrobenzenesulfonic acid derivative in the presence of analkali (e.g. sodium hydroxide), followed by hydrogenation usingpalladium-carbon, to give the corresponding 4,4′-diaminobenzyloxybenzenederivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(5) When X in the general formula (1) is —CH₂OCH₂—:

A 5-chloromethyl-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzenesulfonate) or a2-chloromethyl-5-nitrobenzenesulfonic acid derivative (e.g. sodium2-chloromethyl-5-nitrobenzenesulfonate) is reacted with a5-hydroxymethyl-2-nitrobenzenesulfonic acid derivative or a2-hydroxymethyl-5-nitrobenzenesulfonic acid derivative in the presenceof an alkali (e.g. sodium hydroxide), followed by hydrogenation usingpalladium-carbon, to give the corresponding 4,4′-diaminodibenzyl etherderivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(6) When X in the general formula (1) is —O—:

A 5-hydroxy-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-hydroxy-2-nitrobenzenesulfonate) or a 2-hydroxy-5-nitrobenzenesulfonicacid derivative (e.g. sodium 2-hydroxy-5-nitrobenzenesulfonate) isreacted with a 5-chloro-2-nitrobenzenesulfonic acid derivative or a2-chloro-5-nitrobenzenesulfonic acid derivative in the presence of analkali (e.g. sodium hydroxide), followed by hydrogenation usingpalladium-carbon, to give the corresponding 4,4′-diaminodiphenyl etherderivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(7) When X in the general formula (1) is —S—:

Phenyl sulfide is nitrated using nitric acid and sulfuric acid and thensulfonated using oleum, further followed by hydrogenation usingpalladium carbon, to give a 4,4′-diaminodiphenyl sulfide derivative.This is diazotized using sodium nitrite under acidic conditions in thepresence of hydrochloric acid, followed by reaction with sodium azide,to give the desired product.

(8) When X in the general formula (1) is —SO₂—:

Phenyl sulfide is oxidized using m-chloroperbenzoic acid, then nitratedusing nitric acid and sulfuric acid, and sulfonated using oleum, furtherfollowed by hydrogenation using palladium-carbon, to give a4,4′-diaminodiphenyl sulfone derivative. This is diazotized using sodiumnitrite under acidic conditions in the presence of hydrochloric acid,followed by reaction with sodium azide, to give the desired product.

2. When Z in the general formula (1) is —SO₃ ⁻.Q⁺ (Q⁺ being N⁺R₄)

Those compounds in which Z is —SO₃ ⁻.Q(Q⁺ being Li⁺, Na⁺ or K⁺) asobtained as mentioned above under 1. are acidified with hydrochloricacid and then reacted with HO⁻.N⁺R₄, to give the desired products.

3. When Z in the general formula (1) is —COO⁻.Q⁺ (Q⁺ being Li⁺, Na⁺ orK⁺)

(1) When X in the general formula (1) is a direct bond:

A 2-nitrobenzoic acid derivative (e.g. sodium 2-nitrobenzoate) or a3-nitrobenzoic acid derivative (e.g. sodium 3-nitrobenzoate) is treatedwith zinc dust in the presence of an alkali (e.g. sodium hydroxide), andthe resulting hydrazobenzene derivative is treated with sulfuric acid togive the corresponding 4,4′-diaminobiphenyl derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(2) When X in the general formula (1) is a methylene group:

An 2-anilinecarboxylic acid derivative (e.g. sodium2-anilinecarboxylate) or an 3-anilinecarboxylic acid derivative (e.g.sodium 3-anilinecarboxylate) is treated with formalin under acidicconditions to give the corresponding 4,4′-diaminodiphenylmethanederivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(3) When X in the general formula (1) is an alkylene group containing 2to 5 carbon atoms:

A 2-nitrobenzoic acid derivative (e.g. sodium 2-nitrobenzoate) or a3-nitrobenzoic acid derivative (e.g. sodium 3-nitrobenzoate) is treatedwith a C₂₋₅ α, ω-dichloroalkylene in the presence of aluminum chloride,followed by hydrogenation using palladium-carbon, to give thecorresponding 4,4′-diaminodiphenyl-C₂₋₅-aklyene derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(4) When X in the general formula (1) is —CH₂O— or —OCH₂—:

A 5-chloromethyl-2-nitrobenzoic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzoate) or a 2-chloromethyl-5-nitrobenzoic acidderivative (e.g. sodium 2-chloromethyl-5-nitrobenzenoate) is reactedwith a 5-hydroxy-2-nitrobenzoic acid derivative or a2-hydroxy-5-nitrobenzoic acid derivative in the presence of an alkali(e.g. sodium hydroxide), followed by hydrogenation usingpalladium-carbon, to give the corresponding 4,4′-diaminobenzyloxybenzenederivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(5) When X in the general formula (1) is —CH₂OCH₂—:

A 5-chloromethyl-2-nitrobenzoic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzenoate or a 2-chloromethyl-5-nitrobenzoic acidderivative (e.g. sodium 2-chloromethyl-5-nitrobenzoate) is reacted witha 5-hydroxymethyl-2-nitrobenzoic acid derivative or a2-hydroxymethyl-5-nitrobenzoic acid derivative in the presence of analkali (e.g. sodium hydroxide), followed by hydrogenation usingpalladium-carbon, to give the corresponding 4,4′-diaminodibenzyl etherderivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(6) When X in the general formula (1) is —O—:

A 5-hydroxy-2-nitrobenzoic acid derivative (e.g. sodium5-hydroxy-2-nitrobenzoate) or a 2-hydroxy-5-nitrobenzenesulfonic acidderivative (e.g. sodium 2-hydroxy-5-nitrobenzoate) is reacted with a 5chloro-2-nitrobenzoic acid derivative or a 2-chloro-5-nitrobenzoic acidderivative in the presence of an alkali (e.g. sodium hydroxide),followed by hydrogenation using palladium-carbon, to give thecorresponding 4,4′-diaminodiphenyl ether derivative. This is diazotizedusing sodium nitrite under acidic conditions in the presence ofhydrochloric acid, followed by reaction with sodium azide, to give thedesired product.

(7) When X in the general formula (1) is —S—:

Phenyl sulfide is dibrominated using bromine and then carboxylated usingcarbon monoxide and a palladium catalyst. After subsequent nitrationusing nitric acid and sulfuric acid, hydrogenation is effected usingpalladium-carbon, to give a 4,4′-diaminodiphenyl sulfide derivative.This is diazotized using sodium nitrite under acidic conditions in thepresence of hydrochloric acid, followed by reaction with sodium azide,to give the desired product.

(8) When X in the general formula (1) is —SO₂—:

Phenyl sulfide is oxidized with m-chloroperbenzoic acid, thendibrominated using bromine, and carboxylated using carbon monoxide and apalladium catalyst. After subsequent nitration using nitric acid andsulfuric acid, hydrogenation is effected using palladium-carbon, to givea 4,4′-diaminodiphenyl sulfone derivative. This is diazotized usingsodium nitrite under acidic conditions in the presence of hydrochloricacid, followed by reaction with sodium azide, to give the desiredproduct.

4. When Z in the general formula (1) is —COO⁻.Q⁺ (Q⁺ being N⁺R₄)

Those compounds in which Z is —COO⁻.Q⁺ (Q⁺ being Li⁺, Na⁺ or K⁺) asobtained as mentioned above under 3. are acidified with hydrochloricacid and then reacted with HO⁻.N⁺R₄, to give the desired products.

5. When Z in the general formula (1) is —SO₂NR₂

Those compounds in which Z is —SO₃ ⁻.Q⁺ as obtained as mentioned aboveunder 1. are reacted with phosphorus pentachloride and then reacted withR₂NH in the presence of a tertiary amine (e.g. pyridine) to give thedesired products.

6. When Z in general formula (2) is —SO₃ ⁻.Q⁺ (Q⁺ being Li⁺, Na⁺ or K⁺)

(1) When X in general formula (2) is a direct bond:

A 2-nitrobenzenesulfonic acid derivative (e.g. sodium2-nitrobenzenesulfonate) or a 3-nitrobenzenesuflonic acid derivative(e.g. sodium 3-nitrobenzenesulfonate) and nitrobenzene are treated withzinc dust in the presence of an alkali (e.g. sodium hydroxide) and theresulting hydrazobenzene derivative is treated with sulfuric acid, togive the corresponding 4,4′-diaminobiphenyl derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(2) When X in general formula (2) is a methylene group:

An 2-anilinesulfonic acid derivative (e.g. sodium 2-anilinesulfonate) oran 3-anilinesulfonic acid derivative (e.g. sodium 3-anilinesulfonate)and aniline are treated with formalin under acidic conditions, to givethe corresponding 4,4′-diaminodiphenylmethane derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(3) When X in general formula (2) is an alkylene group containing 2 to 5carbon atoms:

A 2-nitrobenzenesulfonic acid derivative (e.g. sodium2-nitrobenzenesulfonate) or a 3-nitrobenzenesulfonic acid derivative(e.g. sodium 3-nitrobenzenesulfonate) and nitrobenzene are treated witha C₂₋₅ α, ω-dichloroalkylene in the presence of aluminum chloride,followed by hydrogenation using palladium-carbon, to give thecorresponding 4,4′-diaminodiphenyl-C₂₋₅-alkylene derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(4) When X in general formula (2) is —CH₂O—:

A 5-chloromethyl-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzenesulfonate) or a2-chloromethyl-5-nitrobenzenesulfonic acid derivative (e.g. sodium2-chloromethyl-5-nitrobenzenesulfonate) is reacted with 4-nitrophenol inthe presence of an alkali (e.g. sodium hydroxide), followed byhydrogenation using palladium-carbon, to give the corresponding4,4′-diaminobenzyloxybenzene derivative. This is diazotized using sodiumnitrite under acidic conditions in the presence of hydrochloric acid,followed by reaction with sodium azide, to give the desired product.

(5) When X in general formula (2) is OCH₂—:

4-Hydroxymethyl-nitrobenzene is reacted with a5-chloro-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-chloro-2-nitrobenzenesulfonate) or a 2-chloro-5-nitrobenzenesulfonicacid derivative (e.g. sodium 2-chloro-5-nitrobenzenesulfonate) in thepresence of an alkali (e.g. sodium hydroxide), followed by hydrogenationusing palladium-carbon, to give the corresponding4,4′-diaminobenzyloxybenzene derivative. This is diazotized using sodiumnitrite under acidic conditions in the presence of hydrochloric acid,followed by reaction with sodium azide, to give the desired product.

(6) When X in general formula (2) is —CH₂OCH₂—:

A 5-chloromethyl-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzenesulfonate) or a2-chloromethyl-5-nitrobenzenesulfonic acid derivative (e.g. sodium2-chloromethyl-5-nitrobenzenesulfonate) is reacted with4-hydroxymethylnitrobenzene in the presence of an alkali (e.g. sodiumhydroxide), followed by hydrogenation using palladium-carbon, to givethe corresponding 4,4′-diaminodibenzyl ether derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(7) When X in general formula (2) is —O—:

A 5-hydroxy-2-nitrobenzenesulfonic acid derivative (e.g. sodium5-hydroxy-2-nitrobenzenesulfonate) or a 2-hydroxy-5-nitrobenzenesulfonicacid derivative (e.g. sodium 2-hydroxy-5-nitrobenzenesulfonate) isreacted with 4-chloronitrobenzene in the presence of an alkali (e.g.sodium hydroxide), followed by hydrogenation using palladium-carbon, togive the corresponding 4,4′-diaminodiphenyl ether derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(8) When X in general formula (2) is —S—:

Phenyl sulfide is nitrated using nitric acid and sulfuric acid and thenmonosulfonated using oleum, further followed by hydrogenation usingpalladium-carbon, to give a 4,4′-diaminodiphenyl sulfide derivative.This is diazotized using sodium nitrite under acidic conditions in thepresence of hydrochloric acid, followed by reaction with sodium azide,to give the desired product.

(9) When X in general formula (2) is —SO₂—:

Phenyl sulfide is oxidized using m-chloroperbenzoic acid, then nitratedusing nitric acid and sulfuric acid and monosulfonated using oleum,further followed by hydrogenation using palladium-carbon, to give a4,4′-diaminodiphenyl sulfone derivative. This is diazotized using sodiumnitrite under acidic conditions in the presence of hydrochloric acid,followed by reaction with sodium azide, to give the desired product.

7. When Z in general formula (2) is —SO₃ ⁻.Q⁺ (Q⁺ being N⁺R₄)

These compounds in which Z is —SO₃ ⁻.Q⁺ (Q⁺ being Li+, Na⁺ or K⁺) asobtained as described above under 6. are rendered acidic usinghydrochloric acid and then reacted with HO⁻.N⁺R₄ to give the desiredcompounds.

8. When Z in general formula (2) is —COO⁻.Q⁺ (Q⁺ being Li⁺, Na⁺ or K⁺)

(1) When X in general formula (2) is a direct bond:

A 2-nitrobenzoic acid derivative (e.g. sodium 2-nitrobenzoate) or a3-nitrobenzoic acid derivative (e.g. sodium 3-nitrobenzoate) andnitrobenzene are treated with zinc dust in the presence of an alkali(e.g. sodium hydroxide) and the resulting hydrazobenzene derivative istreated with sulfuric acid, to give the corresponding4,4′-diaminobiphenyl derivative. This is diazotized using sodium nitriteunder acidic conditions in the presence of hydrochloric acid, followedby reaction with sodium azide, to give the desired product.

(2) When X in general formula (2) is a methylene group:

An 2-anilinecarboxylic acid derivative (e.g. sodium2-anilinecarboxylate) or an 3-anilinecarboxylic acid derivative (e.g.sodium 3-anilinecarboxylate) and aniline are treated with formalin underacidic conditions to give the corresponding 4,4′-diaminodiphenylmethanederivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(3) When X in general formula (2) is an alkylene group containing 2 to 5carbon atoms:

A 2-nitrobenzoic acid derivative (e.g. sodium 2-nitrobenzoate) or a3-nitrobenzoic acid derivative (e.g. sodium 3-nitrobenzoate) andnitrobenzene are treated with a C₂₋₅ α, ω-dichloroalkylene in thepresence of aluminum chloride, followed by hydrogenation usingpalladium-carbon, to give the corresponding4,4′-diaminodiphenyl-C₂₋₅-alkylene derivative. This is diazotized usingsodium nitrite under acidic conditions in the presence of hydrochloricacid, followed by reaction with sodium azide, to give the desiredproduct.

(4) When X in general formula (2) is —CH₂O—:

A 5-chloromethyl-2-nitrobenzoic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzoate) or a 2-chloromethyl-5-nitrobenzoic acidderivative (e.g. sodium 2-chloromethyl-5-nitrobenzoate) is reacted with4-nitrophenol in the presence of an alkali (e.g. sodium hydroxide),followed by hydrogenation using palladium-carbon, to give thecorresponding 4,4′-diaminobenzyloxybenzene derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(5) When X in general formula (2) is —OCH₂—:

4-Hydroxymethyl-nitrobenzene is reacted with a 5 chloro-2-nitrobenzoicacid derivative (e.g. sodium 5-chloro-2-nitrobenzoate) or a2-chloro-5-nitrobenzoic acid derivative (e.g. sodium2-chloro-5-nitrobenzoate) in the presence of an alkali (e.g. sodiumhydroxide), followed by hydrogenation using palladium-carbon, to givethe corresponding 4,4′-diaminobenzyloxybenzene derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(6) When X in general formula (2) is —CH₂OCH₂—:

A 5-chloromethyl-2-nitrobenzoic acid derivative (e.g. sodium5-chloromethyl-2-nitrobenzoate) or a 2-chloromethyl-5-nitrobenzoic acidderivative (e.g. sodium 2-chloromethyl-5-nitrobenzoate) is reacted with4-hydroxymethylnitrobenzene in the presence of an alkali (e.g. sodiumhydroxide), followed by hydrogenation using palladium-carbon, to givethe corresponding 4,4′-diaminodibenzyl ether derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(7) When X in the general formula (2) is —O—:

A 5-hydroxy-2-nitrobenzoic acid derivative (e.g. sodium5-hydroxy-2-nitrobenzoate) or a 2-hydroxy-5-nitrobenzoic acid derivative(e.g. sodium 2-hydroxy-5-nitrobenzoate) is reacted with4-chloronitrobenzene in the presence of an alkali (e.g. sodiumhydroxide), followed by hydrogenation using palladium-carbon, to givethe corresponding 4,4′-diaminodiphenyl ether derivative. This isdiazotized using sodium nitrite under acidic conditions in the presenceof hydrochloric acid, followed by reaction with sodium azide, to givethe desired product.

(8) When X in general formula (2) is —S—:

Phenyl sulfide is monobrominated using bromine and carboxylated usingcarbon monoxide and a palladium catalyst. The subsequent nitration iseffected using nitric acid and sulfuric acid, followed by hydrogenationusing palladium-carbon, to give a 4,4′-diaminodiphenyl sulfidederivative. This is diazotized using sodium nitrite under acidicconditions in the presence of hydrochloric acid, followed by reactionwith sodium azide, to give the desired product.

(9) When X in general formula (2) is —SO₂—:

Phenyl sulfide is oxidized using m-chloroperbenzoic acid, thenmonobrominated using bromine, and carboxylated using carbon monoxide anda palladium catalyst. The subsequent nitration is effected using nitricacid and sulfuric acid, followed by hydrogenation usingpalladium-carbon, to give a 4,4′-diaminodiphenyl sulfone derivative.This is diazotized using sodium nitrite under acidic conditions in thepresence of hydrochloric acid, followed by reaction with sodium azide,to give the desired product.

9. When Z in general formula (2) is —COO⁻.Q⁺ (Q⁺ being N⁺R₄)

Those compounds in which Z is —COO⁻.Q⁺ (Q⁺ being Li⁺, Na⁺ or K⁺) asobtained as described above under 8. are acidified with hydrochloricacid and then reacted with HO⁻.N⁺R₄ to give the desired compounds.

10. When Z in general formula (2) is —SO₂NR₂

Those compounds in which Z is —SO₃ ⁻.Q⁺ as obtained as described aboveunder 6. are reacted with phosphorus pentachloride and then with R₂NH inthe presence of a tertiary amine (e.g. pyridine) to give the desiredproducts.

The water-soluble photosensitive compounds of the invention asrepresented by the general formula (1) or (2) can be identified byordinary analytical means, for example by elemental analysis, ¹H-NMR,¹³C-NMR, ultraviolet and/or infrared spectroscopy, and/or massspectrometry.

The water-soluble photosensitive composition of the present inventioncomprises (A) a water-soluble photosensitive compound in which aphotosensitive group has an absorption maximum wavelength of not longerthan 305 nm in the ultraviolet absorption spectrum and (B) awater-soluble vinyl (co)polymer, if necessary together with another orother components. The water-soluble photosensitive compound (A) is notparticularly restricted as long as it has an absorption maximumwavelength of not longer than 305 nm in the ultraviolet absorptionspectrum of the photosensitive group thereof and is soluble in water.Thus, it includes, among others, water-soluble azide compounds,water-soluble diazo compounds and water-soluble photooxidation acidgenerators.

From the resolution viewpoint, water-soluble azide compounds arepreferred and water-soluble azide compounds represented by the abovegeneral formula (1) or (2) are particularly preferred.

The above water-soluble photosensitive compound (A) has a photosensitivegroup showing an absorption maximum wavelength of not longer than 305 nmin the ultraviolet absorption spectrum, with shifting to the shorterwavelength side as compared with the absorption maximum wavelengths(e.g. 335 to 450 nm) of the so-far known stilbene-based azide compounds.Therefore, when pattern forming is carried out using a photosensitivecomposition containing (A) by ultraviolet exposure, the resolution canbe still more improved as compared with photosensitive compositionscontaining a stilbene-derived azide compound.

The absorption maximum wavelength, in the ultraviolet absorptionspectrum, of the photosensitive group(s) of the above water-solublephotosensitive compound (A) is generally not longer than 305 nm and,when the exposure light source is a high pressure mercury lamp orsuper-high pressure mercury lamp, it is preferably 240 to 300 nm fromthe viewpoint of matching between exposure light intensity andresolution.

The amount of (A) to be incorporated in the photosensitive compositionof the invention is generally 1 to 30% by mass, preferably 1 to 20% bymass, based on the mass of the photosensitive composition, from theviewpoint of sensitivity and adhesion.

(A) may comprise a single species or a mixture of two or more species.

The water-soluble vinyl (co)polymer (B) to be used in the water-solublephotosensitive composition of the invention is not particularlyrestricted but includes, among others, N-vinylpyrrolidone (co)polymers,N-vinylformamide (co)polymers, N-vinylacetamide (co)polymers,(meth)acrylamide (co)polymers, N-C₁₋₅-alkyl(meth)acrylamide(co)polymers, N,N-di-C₁₋₅-alkyl(meth)acrylamide (co)polymers,(meth)acrylamide-diacetone (meth)acrylamide copolymers,acryloylmorpholine (co) polymers, acrylamide-2-methylpropanesulfonicacid (co)polymers, vinyl alcohol (co)polymers, sodium styrenesulfonate(co)polymers, (meth)acrylic acid (co)polymers, styrylpyridinium saltcompounds described in Japanese Kokai Publication Sho-55-23163, casein,gelatin, methylcellulose, hydroxypropylcellulose, polyvinylcellulose andpolyethylene glycol.

Preferred among them from the sensitivity viewpoint areN-vinylpyrrolidone (co) polymers, N-vinylformamide (co)polymers,N-vinylacetamide (co)polymers, (meth)acrylamide (co)polymers,N-C₁₋₅-alkyl(meth)acrylamide (co)polymers,N,N-di-C₁₋₅-alkyl(meth)acrylamide (co)polymers,(meth)acrylamide-diacetone (meth)acrylamide copolymers,acryloylmorpholine (co) polymers, acrylamide-2-methylpropanesulfonicacid (co)polymers, vinyl alcohol (co)polymers, sodium styrenesulfonate(co)polymers and (meth)acrylic acid (co)polymers, and, particularlypreferred are N-vinylpyrrolidone (co)polymers, N-vinylformamide(co)polymers, N-vinylacetamide (co)polymers and(meth)acrylamide-diacetone(meth)acrylamide copolymers.

Considering the sensitivity and viscosity of the photosensitivecomposition, the above water-soluble vinyl (co)polymer (B) shouldgenerally have a weight average molecular weight (as determined by GPC)of 50,000 to 2,000,000, preferably 200,000 to 1,500,000.

The amount of (B) to be incorporated is, from the sensitivity andadhesion viewpoint, generally 70 to 99% by mass, preferably 80 to 99% bymass, based on the mass of the photosensitive composition.

(B) may comprise a single species or a mixture of two or more species.

The composition of the invention may contain an adhesion improving agent(C), if necessary for improving the adhesion of the composition to theglass surface. By incorporating (C), it is possible to improve theadhesion to glass. As (C), there may be mentioned silane coupling agents[e.g. amino-containing silane coupling agents such asvinyl-tris(β-methoxyethoxy)silane,N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane,N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,N-β-(aminoethyl)-γ-aminopropyltriethoxysilane,γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane;glycidyl-containing silane coupling agents such asγ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane andγ-glycidoxypropylmethyldiethoxysilane; etc.], titanium coupling agent[e.g. dihydroxybis(lactado)titanium, dialkylbis(triethanolaluminato)titanium, oxotitaniumbis(monoammonium oxalate), etc.], organiccarboxylic acid compounds, organophosphorus compounds and,organophosphate compounds, among others. From the adhesion strengthviewpoint, however, silane coupling agents and titanium coupling agentsare preferred.

The amount of (C), if incorporated, is generally not more than 10% bymass, preferably 0.01 to 5% by mass, from the adhesion effect andresolution viewpoint, based on the mass of (B).

The composition of the present invention may contain a water-solublesolvent as a diluent. By incorporating such a diluent, it becomespossible to adjust the spreadability, storage stability, developmentcharacteristics and adhesiveness of the composition, among others.

The diluent is not particularly restricted but may be any one misciblewith the respective components. Thus, for example, there may bementioned water; alcohol solvents such as methanol, ethanol andisopropyl alcohol; glycol solvents such as methylcellosolve,ethylcellosolve, butylcellosolve, diethylene glycol monomethyl ether anddiethylene glycol monoethyl ether; and amide solvents such asN-methylpyrrolidone, 2-pyrrolidone, dimethylformamide andN,N-dimethylacetamide, among others.

Preferred among them from the sensitivity and resolution viewpoint arewater, alcohol solvents and glycol ether solvents, and, particularlypreferred is water.

The amount of the diluent may be selected arbitrarily according to theconditions of application of the photosensitive composition, amongothers. Generally, however, the diluent is used preferably in an amountof 2 to 100 times, in particular 5 to 70 times, based on the mass of thewater-soluble vinyl (co)polymer.

The photosensitive composition of the invention may further contain asurfactant, if necessary for improving the substrate wetting ability.The surfactant is not particularly restricted but may be any of thosemiscible with the respective components, such as anionic, nonionic andcationic surfactants.

Preferred among them from the stability viewpoint are nonionicsurfactants (e.g. sorbitan ester-ethylene oxide adducts,alkylphenol-ethylene oxide adducts).

When a surfactant is incorporated, the amount thereof is generally notmore than 5% by mass, preferably 0.05 to 3% by mass, based on the massof (B) from the additive effect and developability viewpoint.

The photosensitive composition of the invention may further contain, asnecessary, a low molecular compound having a hydroxy group(s) and/or aniodine atom(s) within the molecule and having a molecular weight of notmore than 990. By incorporating such low molecular compound, it ispossible to adjust the development characteristics and adhesiveness,among others, and further to improve the sensitivity.

As the hydroxy-containing low molecular compounds, there may bementioned n-butanol, ethylene glycol, diethylene glycol, propyleneglycol, 1,3-butylene glycol, 1,5-pentanediol, triethanolamine, glycerol,erythritol, pentaerythritol, sorbitol, hexitol and dipentaerythritol,among others.

As the iodine-containing low molecular compounds, there may bementioned, for example, iodoacetic acid,3,5-diamino-2,4,6-triiodobenzoic acid, sodium3,5-diamino-2,4,6-triiodobenzoate, 3-amino-2,4,6-triiodobenzoic acid,sodium 3-amino-2,4,6-triiodobenzoate, 5-amino-2,4,6-triiodoisophthalicacid, sodium 5-amino-2,4,6-triiodoisophthalate,5-amino-2,4,6-triiodoisophthalamic acid, sodium5-amino-2,4,6-triiodoisophthalamate, 3,5-diiodosalicylic acid, sodium3,5-diiodosalicylate, 2,3,5-triiodobenzoic acid, sodium2,3,5-triiodobenzoate, tetraalkylammonium iodides, sodium iodide andpotassium iodide.

When such hydroxy- and/or iodine-containing low molecular compound isincorporated, the amount thereof is generally 1 to 200% by mass,preferably 1 to 100% by mass, based on the mass of (B) from the additiveeffect and developability viewpoint.

The water-soluble photosensitive compound and water-solublephotosensitive composition of the present invention are highly useful infine pattern forming resists, color cathode ray tube inside surfacepattern forming resists, shadow mask forming etching resists, colorfilter black matrix forming resists, color filter pigment dispersingresists, plasma display panel patterning resists, field emission displaypatterning resists, fluorescent display tube patterning resists, printedcircuit board soldering resists, printed circuit board etching resists,printed circuit board dry film resists, interlayer isolating materials,liquid crystal transparent conductive layer (TO) patterning resists,photosensitive printing plates, printing inks, photocuring coatingcompositions and the like and, in particular, they are very useful infine pattern forming resists and color cathode ray tube-inside surfacepattern forming resists (color cathode ray tube black matrix formingresists, color cathode ray tube fluorescent material patterning resists,color cathode ray tube pigment filter patterning resists, etc.).

As a specific example of the use of the photosensitive composition ofthe present invention, fine pattern formation is explained in thefollowing.

The method of fine pattern formation comprises, for example, thefollowing series of steps:

-   -   Applying the photosensitive composition of the invention to a        glass substrate generally by spin coating or the like technique        to a thickness of 0.1 to 2 μm;    -   Drying the coating using a hot plate, infrared heater, far        infrared heater or the like to form a film;    -   Exposing the film to ultraviolet rays from a super-high pressure        mercury lamp, high pressure mercury lamp, metal halide lamp or        xenon lamp or the like through a photomask having a desired        pattern generally at 0.5 to 100 mJ/cm²; and    -   Developing and removing the unexposed portions by washing.

When the photosensitive composition of the invention is used in colorcathode ray tube black matrix formation, the resolution can further beimproved since the composition has a reciprocity law failure property.

The reciprocity law failure property is the property such that a patternof stripes or dots substantially smaller in area than the light exposureareas is formed on a glass surface in the presence of gaseous oxygen.

The filter and lens, among others, of the exposure apparatus forexposing the photosensitive composition of the invention to ultravioletrays are preferably made of a material showing low light absorption inthe vicinity of 240 to 305 nm, in particular quartz. Soda lime glassfairly absorbs ultraviolet rays not longer than 305 nm in wavelength,hence is not preferred.

BEST MODES FOR CARRYING OUT THE INVENTION

The following examples illustrate the present invention in furtherdetail. They are, however, by no means limitative of the scope of theinvention. In the following, “part(s)” means “part(s) by mass” and “%”means “% by mass”.

The sensibility has various definitions, however, that is defined hereinas the exposure time until the ratio (residual film ratio) of filmthickness after exposure and development under a constant illuminationbecomes 50% relative to the initial thickness. In this case, the shorteris the exposure time, the higher is the sensibility.

EXAMPLE 1 Synthesis of disodium4,4′-diazido-2,2′-methylenedibenzenedisulfonate

(1) 3-Anilinesulfonic acid (10 g, 57.8 mmol) was dissolved in a mixedsolvent composed of 4.5 g of 37% formalin (in water), 20 g ofconcentrated hydrochloric acid (pure substance content 35%) and 20 g ofwater, and the reaction was allowed to proceed at 80° C. for 5 hours.The reaction mixture was allowed to cool, then made alkaline by additionof sodium hydroxide, and poured into 500 ml of acetone, and theresulting solid precipitate was collected by filtration to give 6.7 g(16.7 mmol) of crude disodium4,4′-diamino-2,2′-methylenedibenzenedisulfonate [yield=58%].(2) The crude disodium 4,4′-diamino-2,2′-methylenedibenzenedisulfonateobtained in (1) (6.7 g, 16.7 mmol) was dissolved in a mixed solventcomposed of 100 g of water and 5 g of concentrated hydrochloric acid(pure substance content 35%) and the solution was cooled to 0 to 5° C.To this was added an aqueous solution (5 ml) containing 1.3 g (18.4mmol) of sodium nitrite, and the mixture was further stirred at 0 to 5°C. for 1 hour. To this was added an aqueous solution (5 ml) containing1.1 g (16.7 mmol) of sodium azide at 0 to 5° C., and the mixture wasstirred at room temperature for 5 hours. This reaction mixture was madealkaline by addition of sodium hydroxide and poured into 1,000 ml ofacetone, and the resulting solid precipitate was collected by filtrationand dried to give 6.1 g (12.5 mmol) of disodium4,4′-diazido-2,2′-methylenedibenzenedisulfonate dihydrate [yield=75%].

Elemental analysis

Calculated values: Found values: C: 31.840 C: 31.752 H: 2.467 H: 2.448N: 17.138 N: 17.192

¹H-NMR (ppm); 3.81 (s, 2H), 7.60-7.70 (m, 4H), 8.30 (d, 2H) Absorptionmaximum wavelength: 259 nm.

EXAMPLE 2 Synthesis of disodium4,4′-diazido-3,3′-methylenedibenzenedisulfonate

(1) 2-Anilinesulfonic acid (10 g, 57.8 mmol) was dissolved in a mixedsolvent composed of 4.5 g of 37% formalin (in water), 20 g ofconcentrated hydrochloric acid (pure substance content 35%) and 20 g ofwater, and the reaction was allowed to proceed at 80° C. for 5 hours.The reaction mixture was allowed to cool, then made alkaline by additionof sodium hydroxide, and poured into 500 ml of acetone, and theresulting solid precipitate was collected by filtration to give 7.4 g(18.5 mmol) of crude disodium4,4′-diamino-3,3′-methylenedibenzenedisulfonate [yield=64%].(2) The crude disodium 4,4′-diamino-3,3′-methylenedibenzenedisulfonateobtained in (1) (7.4 g, 18.5 mmol) was dissolved in a mixed solventcomposed of 100 g of water and 5 g of concentrated hydrochloric acid(pure substance content 35%) and the solution was cooled to 0 to 5° C.To this was added an aqueous solution (5 ml) containing 1.4 g (20.4mmol) of sodium nitrite and the mixture was further stirred at 0 to 5°C. for 1 hour. To this was added an aqueous solution (5 ml) containing1.2 g (18.5 mmol) of sodium azide at 0 to 5° C., and the mixture wasstirred at room temperature for 5 hours. The reaction mixture was madealkaline by addition of sodium hydroxide and poured into 1,000 ml ofacetone, and the resulting solid precipitate was collected by filtrationand dried to give 6.2 g (12.6 mmol) of disodium4,4′-diazido-3,3′-methylenedibenzenedisulfonate dihydrate [yield=68%].

Elemental analysis

Calculated values: Found values: C: 31.840 C: 31.892 H: 2.467 H: 2.470N: 17.138 N: 17.089

¹H-NMR (ppm); 3.81 (s, 2H), 7.41 (m, 2H), 7.92-8.11 (m, 4H) Absorptionmaximum wavelength: 262 nm.

EXAMPLE 3 Synthesis of disodium4,4′-diazido-2,2′-(1,2-ethanediylbenzene)disulfonate

(1) Disodium 4,4′-diamino-2,2′-stilbenedisulfonate (20 g, 48.7 mmol) wasdissolved in 150 ml of ethanol, 1.0 g of 5% palladium-carbon was addedthereto, and hydrogenation was effected by stirring the mixture at roomtemperature in a hydrogen atmosphere at ordinary pressure. Afterconfirmation of cessation of hydrogen absorption, the 5%palladium-carbon was filtered off, and the ethanol was distilled offunder reduced pressure to give 18.4 g (44.3 mmol) of crude disodium4,4′-diamino-2,2′-(1,2-ethanediylbenzene)disulfonate [yield=91%].(2) The crude disodium4,4′-diamino-2,2′-(1,2-ethanediylbenzene)disulfonate (18.4 g, 44.3 mmol)was dissolved in a mixed solvent composed of 800 g of water and 13 g ofconcentrated hydrochloric acid (pure substance content 35%), and thesolution was cooled to 0 to 5° C. To this was added an aqueous solution(12 ml) of 3.4 g (48.7 mmol) of sodium nitrite, and the mixture wasfurther stirred at 0 to 5° C. for 1 hour. Thereto was added an aqueoussolution (12 ml) of 2.9 g (44.3 mmol) of sodium azide at 0 to 5° C., andthe mixture was stirred at room temperature for 5 hours. The reactionmixture was made alkaline by addition of sodium hydroxide and thenpoured into 5,000 ml of acetone, and the resulting solid precipitate wascollected by filtration and dried to give 15.6 g (31.0 mmol) of disodium4,4′-diazido-2,2′-(1,2-ethanediylbenzene)disulfonate dihydrate[yield=70%].

Elemental analysis

Calculated values: Found values: C: 33.337 C: 33.319 H: 2.798 H: 2.804N: 16.661 N: 16.642

¹H-NMR (ppm); 2.88 (s, 4H), 7.21-7.38 (m, 4H), 7.88 (d, 2H) Absorptionmaximum wavelength: 258 nm.

EXAMPLE 4 Synthesis of disodium 4,4′-diazido-2,2′-biphenylenedisulfonate

(1) 3-Nitrobenzenesulfonic acid (10 g, 49.3 mmol) was dissolved in 40 mlof ethanol, 25 g of zinc dust was added thereto, and the mixture washeated under reflux. While continuing the refluxing, an aqueous solutionof sodium hydroxide (15 g/50 ml) and 40 ml of ethanol were added in thatorder, and the refluxing was conducted for 2 hours. Zinc dust (5 g) wasthen added and the refluxing was further continued for 4 hours.Thereafter, the reaction mixture was poured into 150 ml of a 30% aqueoussolution of acetic acid supplemented with 0.5 g of sodium nitrite, andthe solid obtained was washed with ethanol and dried to give 7.8 g (22.7mmol) of crude hydrazobenzene-3,3′-sulfonic acid [yield=92%].(2) The crude hydrazobenzene-3,3′-sulfonic acid (7.8 g, 22.7 mmol)obtained in (1) was dissolved in 50 ml of ether followed by addition of35 ml of concentrated hydrochloric acid (pure substance content 35%),and the mixture was stirred vigorously at room temperature for 1 hour.The precipitate solid was collected by filtration, washed with ether andthen added to 100 ml of a 10% aqueous solution of sodium hydroxide, andthe mixture was stirred at 80° C. for 1 hour. After allowing to cool,the reaction mixture was extracted with ether, and the ether was thenremoved to give 6.3 g (16.1 mmol) of crude disodium4,4′-diamino-2,2′-biphenylenedisulfonate [yield=71%].(3) The crude disodium 4,4′-diamino-2,2′-biphenylenedisulfonate (6.3 g,16.1 mmol) obtained in (2) was dissolved in a mixed solvent composed of100 g of water and 5 g of concentrated hydrochloric acid (pure substancecontent 35%), and the mixture was cooled to 0 to 5° C. To this was addedan aqueous solution (5 ml) containing 1.2 g (17.7 mmol) of sodiumnitrite, and the mixture was further stirred at 0 to 5° C. for 1 hour.Then, an aqueous solution (5 ml) containing 1.0 g (16.1 mmol) of sodiumazide was added at 0 to 5° C. and the whole mixture was stirred at roomtemperature for 5 hours. This reaction mixture was made alkaline byaddition of sodium hydroxide and then poured into 1,000 ml of acetone.The resulting precipitate solid was collected by filtration and dried togive 4.8 g (10.1 mmol) of disodium4,4′-diazido-2,2′-biphenylenedisulfonate dihydrate [yield=63%].

Elemental analysis

Calculated values: Found values: C: 30.257 C: 30.271 H: 2.116 H: 2.111N: 17.642 N: 17.621

¹H-NMR (ppm); 7.32 (m, 2H), 7.76-7.99 (m, 4H) Absorption maximumwavelength: 262 nm.

EXAMPLE 5

According to the formulation shown below, the specified components weremixed up to give a photosensitive composition (1) of the invention. Thecomposition (1) was applied to a glass substrate to a film thickness of0.5 μm by spin coating and then dried on a hot plate at 50° C. for 1minute to form a coat film. Then, this film was exposed to ultravioletrays at an exposure illuminance of 2.5 mW/cm² through a 50 μm line widthphotomask using a proximity exposure machine equipped with a super-highpressure mercury lamp. The proximity gap was set at 50 μm. Thereafter,development was carried out using water at ordinary temperature tothereby form a resist pattern, and the sensitivity was determined. Thesensitivity was 1.0 second (luminous exposure: 2.5 mJ/cm²).

Exposure to ultraviolet rays was also carried out using Sharpness TestChart No. 1 (product of Toppan Printing Co.) as the photomask under thefollowing conditions: exposure illuminance 2.5 mW/cm², exposure time 10seconds (luminous. exposure 25 mJ/cm², proximity gap 50 μm. Thereafter,development was effected with water at ordinary temperature to therebyform a resist pattern, and the resolution was determined. The resolutionwas 5 μm.

[Formulation of photosensitive composition (1)]

Aqueos solution of polyvinylformamide   10 parts (“PNVF 0500”, productof Mitsubishi Chemical) (solid concentration = 30%) Photosensitivecompound obtained in  0.3 part Example 1 Surfactant (“Nonipol 100”,product of 0.03 part Sanyo Chemical Industries) Silane coupling agent(“KBM-603”, product 0.03 part of Shin-Etsu Chemical)] Water  100 parts

EXAMPLE 6

A photosensitive composition (2) was prepared according to theformulation shown below. Using it, a resist pattern was formed by itsapplication, drying, exposure and development with water at ordinarytemperature and the sensitivity was measured in the same manner as inExample 5. The sensitivity was 1.5 seconds (luminous exposure: 3.8mJ/cm²).

The resolution was measured in the same manner as in Example 5 and foundto be 5 μm.

[Formulation of photosensitive composition (2)]

Aqueous solution of polyvinylpyrrolidone   30 parts (“PVP K-90”, productof ISP) (solid concentration = 10%) Photosensitive compound obtained in 0.3 part Example 1 Surfactant (“Nonipol 100”, product of 0.03 partSanyo Chemical Industries) Silane coupling agent (“KBM-603”, product0.03 part of Shin-Etsu Chemical) Water   80 parts

COMPARATIVE EXAMPLE 1

A photosensitive composition for comparison (Compar. 1) was preparedaccording to the formulation shown below. Using it, a resist pattern wasformed by its application, drying, exposure and development with waterat ordinary temperature and the sensitivity was measured in the samemanner as in Example 5. The sensitivity was 2.5 seconds (luminousexposure: 6.3 mJ/cm²).

The resolution was measured in the same manner as in Example 5 and foundto be 15 μm.

[Formulation of photosensitive composition (Compar. 1)]

Aqueous solution of polyvinylpyrrolidone   30 parts (“PVP K-90”, productof ISP) (solid concentration = 10%) Disodium 4,4′-diazidostilbene-2-2′- 0.3 part disulfonate Surfactant (“Nonipol 100”, product of 0.03 partSanyo Chemical Industries) Silane coupling agent (“KBM-603”, product0.03 part of Shin-Etsu Chemical) Water   80 parts

INDUSTRIAL APPLICABILITY

The photosensitive compound and photosensitive composition of theinvention produce the following effects and have very high utility.

1) The photosensitive compound of the invention has an absorptionmaximum wavelength of less than 305 nm, and a photosensitive compositioncontaining said photosensitive compound is very high in resolution, inparticular in resolution in proximity exposure, hence enables formationof fine patterns with high dimension accuracy.

2) Such hazardous substances as chromium compounds are not contained, sothat no equipment is required for removing such hazardous substances inwaste water, hence no environmental pollution results.

1. A water-soluble photosensitive compound represented by the followinggeneral formula (1):

in the formula, X represents an alkylene group containing 1 to 5 carbonatoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂—, Z represents —SO₃⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺, Na⁺, K⁺ or N⁺R₄,and R represents a hydrogen atom and/or an alkyl group containing 1 to 5carbon atoms, and said alkyl group optionally having one hydroxy, ether,carbonyl, carbonyloxy or oxycarbonyl group, and the two Z groups may bethe same or different or by the following general formula (2):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, or —SO₂— and Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄ and R represents a hydrogen atom and/or an alkyl groupcontaining 1 to 5 carbon atoms, said alkyl group optionally having onehydroxy, ether, carbonyl carbonyloxy or oxycarbonyl group, wherein aphotosensitive group has an absorption maximum wavelength of not longerthan 305 nm the ultraviolet absorption spectrum thereof.
 2. Thewater-soluble photosensitive compound according to claim 1, wherein aphotosensitive group has an absorption maximum wavelength, in theultraviolet absorption spectrum, of 240 to 300 nm.
 3. The water-solublephotosensitive compound according to claim 1, wherein X in generalformula (1) is a methylene group or an ethylene group, and X in generalformula (2) is a directed bond, a methylene group or an ethylene group.4. The water-soluble photosensitive compound accordog to claim 1,wherein Z in general formula (1) or (2) is —SO₃ ⁻.Q⁺, said Q⁺ being Li⁺,Na⁺, K⁺ or N⁺R₄, said R representing a hydrogen atom and/or an alkylgroup containing 1 to 5 carbon atoms, and said alkyl group optionallyhaving one hydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group.5. The water-soluble photosensitive compound according to claim 1,wherein said compound is disodium4,4′-diazido-2,2′-methylenedibenzenedisulfonate, disodium4,4′-diazido-3,3′-methylenedibenzenedisulfonate, disodium4,4′-diazido-2,2′-(1,2-ethanediyldibenzene)disulfonate or disodium4,4′-diazido-3,3′-(1,2-ethanediyldibenzene)disulfonate.
 6. Aphotosensitive compostion comprising 1 to 30% by mass of a water-solublephotosensitive compound (A) and 70 to 99% by mass of a water-solublevinyl (co)polymer (B), wherein a photosensitive group in said (A) has anabsorption maximum wavelength of not longer than 305 nm in theultraviolet absorption spectrum thereof wherein said water-solublephotosensitive compound (A) is represented by the following generalformula (1):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO—, Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄ and R represents a hydrogen atom and/or an alkyl groupcontaining 1 to 5 carbon atoms, said alkyl group optionally having onehydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group, and the twoZ groups may be the same or different or by the following generalformula (2):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂— and Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄ and R represents a hydrogen atom and/or an alkyl groupcontaining 1 to 5 carbon atoms, said alkyl group optionally having onehydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group, wherein thecompound of the general formula (1) is disodium4,4′-diazido-2,2′-biphenylenedisulfonate when X in the general formula(1) represents a direct bond.
 7. The photosensitive compositionaccording to claim 6, wherein a photosensitive group of saidwater-soluble photosensitive compound (A) has an absorption maximumwavelength, in the ultraviolet absorption spectrum, of 240 to 300 nm. 8.The photosensitive composition according to claim 6, wherein saidwater-soluble photosensitive compound (A) is a water-soluble azidecompound.
 9. The photosensitive composition according to claim 6,wherein X in general formula (1) or (2) is a direct bond, a methylenegroup or an ethylene group.
 10. The photosensitive composition accordingto claim 6, wherein Z in general formula (1) or (2) is —SO₃ ⁻.Q⁺, saidQ⁺ being Li⁺, Na⁺, K⁺ or N⁺R₄, R representing a hydrogen atom and/or analkyl group containing 1 to 5 carbon atoms, and said alkyl groupoptionally having one hydroxy, ether, carbonyl, carbonyloxy oroxycarbonyl group.
 11. The photosensitive composition according to claim6, wherein the water-soluble vinyl (co)polymer (B) comprises at leastone member selected from the group consisting of N-vinylpyrrolidone(co)polymers, N-vinylformamide (co)polymers, N-vinylacetamide(co)polymers (meth)acrylamide (co)polymers,N-C₁₋₅-alkyl(meth)acrylamide, N,N-di-C₁₋₅-alkyl(meth)acrylamide,(meth)acrylamide-diacetone(meth)acrylamide copolymers,acryloylmorpholine (co)polymers, acrylamide-2-methylpropanesulfonic acid(co)polymers, vinyl alcohol (co)polymers, sodium styrenesulfonate(co)polymers and (meth)acrylic acid (co)polymers.
 12. The photosensitivecomposition according to claim 6 which comprises 0.01 to 10% by mass,based on the mass of said water-soluble vinyl (co)polymer (B), of anadhesion improving agent (C).
 13. The photosensitive compositionaccording to claim 6 which has a reciprocity law failure property. 14.The photosensitive composition according to claim 6 being suitable foruse in color cathode ray tube inside surface pattern formation.
 15. Thephotosensitive composition according to claim 14, wherein the insidesurface pattern formation is black matrix formation.
 16. Thewater-soluble photosensitive compound according to claim 2, wherein X ingeneral formula (1) a methylene group or an ethylene group, and X ingeneral formula (2) is a direct bond, a methylene group or an ethylenegroup.
 17. The water-soluble photosensitive compound according to claim2, wherein Z in general formula (1) or (2) is —SO₃ ⁻.Q⁺, said Q⁺ beingLi⁺, Na⁺, K⁺ or N⁺R₄, said R representing a hydrogen atom and/or analkyl group containing 1 to 5 carbon atoms, and said alkyl groupoptionally having one hydroxy, ether, carbonyl, carbonyloxy oroxycarbonyl group.
 18. The water-soluble photosensitive compoundaccording to claim 3, wherein Z in general formula (1) or (2) is —SO₃⁻.Q⁺, said Q⁺ being Li⁺, Na⁺, K⁺ or N⁺R₄, said R representing a hydrogenatom and/or an alkyl group containing 1 to 5 carbon atoms, and saidalkyl group optionally having one hydroxy, ether, carbonyl, carbonyloxyor oxycarbonyl group.
 19. The water-soluble photosensitive compoundaccording to claim 2, wherein said compound is disodium4,4′-diazido-2,2′-methylenedibenzenedisulfonate, disodium4,4′-diazido-3,3′-methylenedibenzenedisulfonate, disodium4,4′-diazido-2,2′-(1,2-ethanediyldibenzene)disulfonate or disodium4,4′-diazido-3,3′-(1,2-ethanediyldibenzene)disulfonate.
 20. A method forproducing a color cathode ray tube, comprising forming a inside surfacepattern of said tube by using a photosensitive composition as a resist,wherein said photosensitive composition comprises 1 to 30% by mass of awater-soluble photosensitive compound (A) and 70 to 99% by mass of awater-soluble vinyl (co)polymer (B), wherein said water-solublephotosensitive compound (A) is represented by the following generalformula (1):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂—, Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄, and R represents a hydrogen atom and/or an alkyl groupcontaining 1 to 5 carbon atoms, and said alkyl group optionally havingone hydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group, and thetwo Z groups may be the same or different or by the following generalformula (2):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂— and Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄ and R represents a hydrogen atom and/or an alkyl groupcontain 1 to 5 carbon atoms, said alkyl group optionally having onehydroxy, ether, carbonyl, carbonyloxy or oxycarbonyl group, wherein aphotosensitive group in said compound (A) has an absorption maximumwavelength of not longer than 305 nm in the ultraviolet absorptionspectrum thereof.
 21. A color cathode ray tube obtained by forming ainside surface pattern of said tube by using a photosensitivecomposition as a resist, wherein said photosensitive compositioncomprises 1 to 30% by mass of a water-soluble photosensitive compound(A) and 70 to 99% by mass of a water-soluble vinyl (co)polymer (B),wherein said water-soluble photosensitive compound (A) is represented bythe following general formula (1):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂—, Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄, and R a hydrogen atom and/or an alkyl group containing1 to 5 carbon atoms, and said alkyl group optionally having one hydroxy,ether, carbonyl, carbonyloxy or oxycarbonyl group, and the two Z groupsmay be the same or different or by the following general formula (2):

in the formula, X represents a direct bond, an alkylene group containing1 to 5 carbon atoms, —CH₂O—, —OCH₂—, —CH₂OCH₂—, —O—, —S— or —SO₂—, Zrepresents —SO₃ ⁻.Q⁺, —COO⁻.Q⁺ or —SO₂NR₂, in which Q⁺ represents Li⁺,Na⁺, K⁺ or N⁺R₄, and R a hydrogen atom and/or an alkyl group containing1 to 5 carbon atoms, and said alkyl group optionally having one hydroxy,ether, carbonyl, carbonyloxy or oxycarbonyl group, wherein aphotosensitive group in said compound (A) has an absorption maximumwavelength of not longer than 305 nm in the ultraviolet absorptionspectrum thereof.